Capillary active substances



Patented Nov. 30, 1943 UNITED STATES PATENT OFFICE 2,335,447 I CAPILLARY ACTIVE SUBSTANCES Hillary Robinette, Jr., Arlington, Mass, assignor to Commercial Solvents Corporation, Torre Haute, Ind., a corporation of Maryland No Drawing. Application August 14, 1942, Serial No. 454,781

11 Claims.

My invention relates to new and useful surface active materials, and more particularly it is concerned with a series of compounds of a general type which so far as I am aware, have never been recognized as possessing wetting and penetrating properties, as well as other surface ac tive characteristics. Specifically these products are substituted 1,3-dioxanes which may be represented bv the following structural formula:

NH: CHzOH in which X represents a substituent selected from the group consisting of cycloalkylidene, alkylidene, substituted-cycloalkylidene, or the disubstituted methylene group wherein R and R may be either alkyl, aryl, or

employed in small quantities to secure an effect.

which is principally the result of a wetting action, such as the effect obtained by the presence of a surface active agent at a water-oil interface. For example, in the textile andleather treating industries there are many instances where wetting and detergent action is highly desirable. As a result, many different agents have been proposed to reduce surface tension and promote wetting. The materials that hav been employed in the past, however, although satisfactory in some respects, have not been uniiormly successful.

The ordinary soaps, although their surface active properties have long been recognized, are

deficient in many respects when employed as de-- tergent and wetting agents. For example, although soaps act efliciently as detergents in weakly alkaline solutions, they are of no value for this purpose in acid media, since under such circumstances the free fatty acid, which is insoluble in water, is liberated. In strongly alkaline solutions, on the other .hand, ordinary soaps become insoluble and are salted out of solution. In addition, in the presence of solutions containing calcium or magnesium salts such as ordinary hard water, the fatty acid' present in the soap is precipitated as a calcium or magnesium soap, such soaps being insoluble, sticky materials, which, rather than having any detergent action, are regarded as undesirable impurities in solutions employed in the textile and related industries.

In an effort to furnish materials free from the undesirable properties of ordinary soaps, to such industries, there have been developed as detergent and wetting agents, products obtained by- -sulfonation of certain fatty acids appearing in oils and fats. ,Such fatty acids are characterized by containing unsaturated linkages and/or hydroxyl groups in the molecule. On sulfonating such acids, products are obtained which contain sulfuric ester groups in the molecule, and, of course, carboxylic acid groups are attached to the terminal carbon atoms. The products, however, in general possess weaker wetting and detergent'properties than soaps. Such products are also relatively unstable, and are capable of being decomposed by hydrolysis.

Other proposed wetting agents comprise the semiand compIetely-esterified products resulting from the esterification of a higher alcohol with an unsaturated polybasic acid. After the unsaturated esterified acid is produced, it is converted intoa more soluble form, ordinarily by treatment with sodium bisulfite to yield the corresponding sulfo derivative of the esterified polybasic acid. While such materials have met with with the tendency of the textile treating baths,

containing such materials, to foam.

I have now discovered that aminodioxanes of the class indicated above, serve as highly satisfactory wetting agents, particularly where prior wetting and detergent agents, especially of the type mentioned, are of little or no value. For example,- the wetting agents of the present invention are not decomposed either by hard waters or solutions containing appreciable quantities of alkali. My new wetting agents possess the further advantage in that aqueous solutions thereof are water-white liquids, are soluble in most of the common organic solvents.

In general, the quantity of the new wettin agents which may be employed, will be found to vary withthe type of wetting operation under consideration, as'well as with the material to be wetted. For most purposes, however, I have found that these wetting agents may be utilized in amounts of from about 0.15 to 0.60 per cent by weight of the treating bath. In this connection, I have found that in many cases it may be desirable to employ a solubilizing material with the wetting agents of the present invention. In such instances, the quantity of wetting agent employed may be reduced depending of course upon the quantity and type of solubilizing agent employed. Suitable solubilizing materials which may be utilized in combination with my wetting agents, are sulfonated castor oil, sulfonated petr01eum.0iis, sulfonated alkyi aromatic compounds, sulfated esters, sulfated ether alcohols, sulfonated alkyl diphenyls, soaps, and the like. It is to be specifically understood, however, that the expression solubilizing agent includes any material which is capable of increasing the solu- Table Wettin -out Wetting agent fi time %in seconds) 5-amino-5-hydroxymethyl-2,2-dimethyl- 1. 5 28 l,3- dioxaue 4. -am1no-5-hydroxymethyI-2-benzyl -2- v 1. 5 130 methyl-1,3-dioxane 3. 0 fi-amino-5-hydroxymethy1-2,2-(l-methyil. 5

pentamcthylene)-1,3-dioxane 2. 0 5 ammo 5 hydroxymethyl 2, 2 tetramethylene-1,3-dioxane 1. 0 4

1 Instantaneous.

The wetting agents of the present invention may be prepared in accordance with any of several suitable procedures. For example, they may be conveniently synthesized by first preparing the corresponding nitrodioxanes which involve thecondensation of -tris(hydroxymethyl) nitromethane 'with'the desired ketones in the presence of a.

small quantity of an acid catalyst; and, if desired, in the presence of an organic liquid such as benzene or toluene, which is capable of removing the water produced during the reaction in the do not foam. In addition, these materials, which form of a constant boiling mixture. The nitrodioxane thus produced may then be converted to the corresponding amino derivative by subjecting the same to high pressure hydrogenation in the presence of a nickel catalyst and a suitable solvent, such as methanol, at a temperature in the neighborhood of 25-35 C.

As examples of ketones that may be utilized in preparing the aforesaid nitrodioxanes, there may be mentioned acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl benzyl ketone, methyl phenyl ketone, 1,3-diphenyl-2-propanone, cyclohexanone, 2-methylcyclohexanone,

cyclopentanone, benzophenone, and the like.

As previously stated, the wetting agents of the present invention may be used alone-or in combination with certain solubilizing agents, or other detergents for cleansing and scouring vegetable and animal fibers when removing fatty or oily materials therefrom. Also, they may be used as penetrants in flax retting baths. The penetrating power of these new compositions may be utilized to advantage when said compositions are i added to baths containing starchy ferments which are employed for removingsizing from textile materials; These products are also found to function as useful wetting, cleansing,-and penetrating agents in bleaching liquors, such as those used in the kier boiling of cotton goods, and may be added to the lye liquors used for mercerizing cotton goods. They can also be used to assist in twist setting of yarn and in processes of stripping colors.-

Likewise, these new surface active agents possess characteristics which render them valuable in the application of dyestuffs. They may be used as dye-levelling agents due to their wetting and penetrating properties, in neutral or alkaline dyeing baths, and are capable of facilitating dyeing with developed dyes, the dyeing of acetate fibers with insoluble dyes, the dyeing of animal fibers with vat dyes, the dyeing of various synthetic fibers and the dyeing of leather.

It will readily be apparent, from the foregoing. discussion, that the present invention has made available a large group of new surface active materials, and that such agents are adapted for use in numerous industrial processes requiring surface active substances. It will also be evident to those skilled inthe art that many widely difierent embodiments of the present invention exist, and that such embodiments may be utilized without departing from the scope of said invention.

My invention now having been described, what I claim is:

1. Aqueous baths for the wet treatment of textiles, comprising water and an aminodioxane having the formula:

in which X represents a substituent selected from the group consisting of cycloalkylidene, alkylidene, substituted-cycloalkylidene, and

wherein R and R represent members selected ,irom the class consisting of alkyl, aryl, and analky 2. Aqueous baths for the wet treatment of textiles, comprising water and from about 0.15 to 0.60 per cent by weight of the bath of an aminodioxane having the formula:

NH: (EH-20H in which X represents a substituent selected from the group consisting of cycloalkylidene, alkylidene, substituted-cycloalkylidene, and

in which X represents a substituent selected from the group consisting of cycloalkylidene, alkylidene, substituted-cycloalkylidene, and

wherein R and R represent members selected from the class consisting of alkyl, aryl, and aralkyl.

7. A method for the wet treatment of textiles, which comprises subjecting the same to the action of an aqueous solution comprising water and an aminodioxane of the formula:

NH: CHnOH X y in which X represents a-substituent selected from the group consisting of cycloalkylidene, alkylidene substituted-cycloallq lidene, and

wherein R and R represent members selected from the class consisting of alkyl, aryl, and aralkyl.

8. A method for the wet treatment of textiles, which comprises subjecting the same to the action of an aqueous bath comprising water and 5 amino 5-hydroxymethyl-2-methyl-2-phenyl- 1,3-dioxane.

9. A method for the wet treatment of textiles, which comprises subjecting the same to the-action of an aqueous bath comprising water and 5-amino-5-hydroxymethyl-2,2 tetramethylene 1,3-dioxane.

10. A method for the wet treatment of textiles, which comprises subjecting the same to the action of an aqueous bath comprising water and 5 amino 5-hydroxymethyl-2-benzyl-2-methyl- 1,3-dioxane.

11. A method for the wet treatment of textiles; which comprises subjecting the same to the ac-' tion of an aqueous bath comprising water and 5-amino-5-hydroxymethyl-2,2-dimethyl 1,3-d1- 

